Modification of liquid hydrocarbons

ABSTRACT

Specified copolymers of tert-butylstyrene are dissolved in a liquid aliphatic hydrocarbon fuel, especially an aircraft fuel, by the steps of (i) blending the finely-divided copolymer with a non-solvent hydroxylic liquid miscible with the fuel, (ii) mixing the blend into the fuel so as to give a copolymer concentration of 01.-1% by weight, and (iii) dissolving in the fuel so treated an amino compound in an amount of 0.01-0.6 mole per 100 g of copolymer present. The copolymers thus dissolved impart to the fuel a resistance towards mist formation when the fuel is subjected to conditions of shock.

This application is a continuation of Ser. No. 146,411 filed May 5,1980, which is now U.S. Pat. No. 4,292,045.

This invention relates to the modification of liquid hydrocarbonaircraft fuels, with the object of reducing the tendency of the fuels toform mists when subjected to conditions of shock, by dissolving in thema specified type of polymer. More particularly, it relates to a methodwhereby such a polymer may be dissolved in a liquid hydrocarbon fuel bya simple, rapid mixing procedure.

In our British Patent Specification No. 1,384,536 we have described amethod of dissolving a polymer in a liquid hydrocarbon fuel having aflash point not less than 90° F., characterized in that a dispersion ofthe polymer in an organic liquid in which the polymer is insoluble butwith which the fuel is miscible is admixed with the liquid hydrocarbonfuel. Suitable liquids in which the polymer may be dispersed, accordingto that Specification, include polar liquids such as alcohols andglycols where the liquid fuel is an aliphatic hydrocarbon. The purposeof dissolving the polymer in the liquid fuel is that of reducing thetendency of the fuel to form a readily ignitable mist under shockconditions such as those encountered in an aircraft crash. There are,however, substantial practical problems in dissolving the requisiteproportion of polymer (say 0.1-1.0% by weight) in the large quantitiesof fuel which are handled and consumed in everyday aircraft operation.For the reasons explained in the above-mentioned Specification, it isimpracticable to mix polymer and fuel at any stage prior to the actualloading of the fuel into the aircraft, but, if the polymer is to beintroduced into the fuel in the course of that operation, it isnecessary to achieve rapid dissolution of the polymer in view of thehigh flow rate at which refuelling is normally carried out. The methodof British Specification No. 1,384,536 provides an answer to theseproblems which is applicable in many cases, the pre-mixing of thepolymer with the polar liquid affording a significant enhancement of therate of dissolution of the polymer in the fuel.

We find, however, that, when we apply the method of BritishSpecification No. 1,384,536 to the dissolution of certain polymers in,say, aviation kerosene, using a hydroxylic liquid as the dispersionliquid, the dissolution of the polymer is acceptably rapid but theanti-misting properties of the treated fuel thus obtained are inferiorto those of the same fuel in which the same copolymer has been dissolvedby the more time-consuming method of stirring the polymer into the fuelin the absence of any hydroxylic liquid. Polymers which behave in thisway include the copolymers of tert-butylstyrene which are described anddefined in our British Patent Application No. 7,909,483.

We have now found that, in the foregoing circumstances, the anti-mistingproperties of the fuel treated according to Specification No. 1,384,536can be restored substantially to the same level as, or even a higherlevel than, that attained when the hydroxylic carrier liquid is omitted,by dissolving an amine compound in the fuel so treated.

Thus according to the present invention we provide a method fordissolving, in a liquid aliphatic hydrocarbon fuel having a flash pointnot less than 90° F., a copolymer of (i) at least 75% by weight oftert-butylstyrene, (ii) from 1% to 24% by weight of a second monomerselected from the acrylic and methacrylic esters of aliphatic monohydricalcohols containing from 1 to 4 carbon atoms, 2-ethoxyethylmethacrylate, acrylonitrile, vinyl acetate, styrene and vinyltoluene,and (iii) from 1% to 10% by weight of methacrylic acid, the aggregate ofmonomers (i), (ii) and (iii) being 100% and the copolymer having thefollowing characteristics:

(a) it is soluble in AVTUR 50 aviation kerosene;

(b) a 0.3% by weight solution of the copolymer in AVTUR 50 aviationkerosene has a relative viscosity in the range 1.3 to 2.6 and adifferential orifice flow rate in the range 3 to 7 ccs. per 30 seconds.

the terms "soluble", "AVTUR 50", "relative viscosity" and "differentialorifice flow rate" having the respective meanings hereinafter defined,the method consisting in the steps of (A) blending the copolymer infinely divided form with a hydroxylic liquid which is a non-solvent forthe polymer or at most a weak swellant therefor but which is miscible tothe extent of at least 1% by weight with the fuel; (B) mixing the blendof the copolymer and the hydroxylic liquid into the fuel so as to give aconcentration of copolymer in the fuel of from 0.1% to 1% by weight; and(C) dissolving in the fuel so treated from 0.01 to 0.6 mole, based oneach 100 g of copolymer present, of an amino compound.

By "soluble in AVTUR 50" we mean that solutions of the copolymer inAVTUR 50, at all concentrations in the range 0.1% to 1% by weight, are,notwithstanding that they may appear hazy or opalescent, neverthelesshomogeneous in the sense that no gross separation from them of a swollenpolymer phase occurs on standing for 24 hours at 20° C.

By "AVTUR 50" we mean a liquid hydrocarbon fuel complying with U.K.Government Specification D.Eng.RD 2494 (NATO Code No. F-35) and having aflash point not lower than 100° F. AVTUR 50 normally has a viscosity of1.0-1.5 cp at 25° C.

By "relative viscosity" we mean the ratio of (i) the viscosity of the0.3% by weight copolymer solution in AVTUR 50 when measured by themethod of British Standard No. 188:1937 "The Determination of theViscosity of Liquids in C.G.S. Units", Part 2, using a U-tubeviscometer, Size A, at 25° C., to (ii) the viscosity of AVTUR 50 whenmeasured under those same conditions.

By "differential orifice flow rate" we mean the difference between (a)the flow rate of a 0.3% by weight solution of the copolymer in AVTUR 50through a passage of circular cross-section having a square-edgedorifice, the passage having a length of 0.062 inches and a diameter of0.025 inches, and (b) the flow rate through the same said passage of aNewtonian liquid having the same viscosity as that of the copolymersolution referred to in (a) when the said viscosities are measured bythe method of British Standard No. 188:1937, the flow rates beingexpressed as the volume of liquid in ccs. which passes through theorifice during the second period of 30 seconds of flow. Apparatussuitable for carrying out the differential orifice flow ratedetermination may be constructed by appropriately modifying a type A cupaccording to British Standard No. 1733.

The method of the invention is of particular interest in connection withthe dissolution of copolymers as hereinabove defined which, whendissolved in AVTUR 50 at a concentration of 0.3% by weight, have arelative viscosity in the range 1.3 to 2.1 and a differential orificeflow rate in the range 3 to 6 ccs. per 30 seconds.

As stated above, the hydroxylic liquid with which the copolymer isblended, prior to its being introduced into the liquid fuel, must be onewhich does not dissolve the copolymer, or is at most only a weakswellant for the copolymer in the sense that a mixture of the copolymerin the particulate state with the hydroxylic liquid has a paste-likerather than a rubber-like consistency. The hydroxylic liquid must, atthe same time, be miscible with the liquid fuel to the extent of atleast 1% by weight. Suitable hydroxylic liquids satisfying theserequirements include aliphatic monohydric and dihydric alcohols, moreparticularly methanol, ethanol, propanol and 2-ethoxyethanol amongst themonohydric alcohols and propylene glycol, butylene glycol,2-methyl-2:4-pentanediol and diethylene glycol amongst the dihydricalcohols. In general, the suitability of a given hydroxylic liquid maybe determined by simple experimental tests of its swelling power for thecopolymer and its miscibility with the liquid fuel. However, where theliquid fuel is an aviation kerosene such as AVTUR 50, Jet A or a similarfuel, we find that a preferred hydroxylic liquid is2-methyl-2:4-pentanediol. If desired, a mixture of two or more suitablehydroxylic liquids may be employed instead of a single liquid.

The copolymer in finely divided form may be blended with the hydroxylicliquid in step (A) of the method in any suitable way, for example byhand mixing or by mechanical means, e.g. using a heavy duty blender.Where the proportion of copolymer in the blend is low, i.e. of the orderof 15-25% by weight of the total blend, the blend will be of relativelylow viscosity, but at significantly higher proportions the blend mayhave a paste-like consistency. Generally it is preferred to operate at ahigher proportion, say in the range 30% to 40% by weight, since underthese conditions relatively little settlement of the copolymer occurs ifthe blend is allowed to stand or is stored for some time prior to itsbeing mixed with the liquid fuel. Suitable finely divided copolymer mayconveniently be obtained, in the case where the copolymer is made by aprocess of aqueous emulsion polymerisation of monomers, by removal ofthe aqueous phase e.g. by freeze drying or spray drying, but othermethods may be employed such as precipitation of the copolymer fromsolution or comminution of bulk copolymer.

In step (B) of the method, the blend of copolymer and hydroxylic liquidis added to the liquid fuel under conditions of efficient mixing.Preferably an initial period of turbulent mixing into the fuel isfollowed by a period of more gentle agitation; under these conditionsthe blend is rapidly dispersed into the fuel and a clear productresults. The addition may be carried out either batchwise orcontinuously; in view, however, of the interest in achieving effectivemodification of an aircraft fuel during a refuelling operation,continuous addition of the blend is particularly preferred.

In step (C) of the method, there is introduced, into the fuel treatedwith the copolymer in the preceding steps, an amino compound in anamount of from 0.01 to 0.6 mole based on each 100 g of the copolymertaken. Preferably the amount of amino compound is from 0.02 to 0.2 moleper 100 g of copolymer. Suitable amino compounds include the alkylmonoamines containing from 1 to 12 carbon atoms; these may be primary,secondary or tertiary in character. Examples of suitable members of thisclass include methylamine, ethylamine, butylamine and triethylamine.Also suitable are alkanolamines containing from 4 to 10 carbon atoms,such as diethanolamine, triethanolamine and tri-propanolamine, aromaticamines such as aniline and the N-alkylanilines where the alkyl groupcontains from 1 to 4 carbon atoms, and heterocyclic amines such aspiperidine and morpholine. The preferred amino compounds are the primaryaliphatic amines containing from 3 to 10 carbon atoms, in particularn-butylamine. If desired, a mixture of two or more suitable aminocompounds may be used instead of a single amino compound.

The amount of the amino compound must, as already stated, be at least0.01 mole per 100 g of copolymer taken, in order to ensure that theliquid fuel being treated according to steps (A) and (B) develops asatisfactory degree of resistance to misting under shock conditions. Inthe presence of any smaller proportion than this of the amino compound,or in its complete absence, admixture of the copolymer-hydroxylic liquidblend with the fuel results in dissolution of the copolymer but theanti-misting properties of the solution are relatively slight. Theoptimum amount of amino compound will normally lie significantly abovethis lower limit, but below the upper limit previously stated of 0.6mole per 100 g of copolymer.

There are two alternative ways in which the amino compound may beintroduced. On the one hand, it may be added in step (C) as a separateoperation subsequent to completion of step (B); on the other hand, itmay be added to the liquid fuel simultaneously with the blend of thecopolymer and the hydroxylic liquid, in other words, by carrying outsteps (B) and (C) together. From a procedural point of view, the secondof these alternatives is to be preferred since it enables a quantity ofaircraft fuel to be modified in a single operation, i.e. by a "one-shot"addition of the three active materials. Under these circumstances,however, the optimum amount of amino compound will usually represent acompromise, inasmuch as an increase in the amount of the amino compound,whilst it enhances the anti-misting properties of the treated fuel,tends to slow down the rate of dissolution of the copolymer in the fuel.In practice it is a matter of simple experimental trial to select theoptimum proportions of copolymer, hydroxylic liquid and amino compoundin any given case. Employing the proportions thus established, a"one-shot" treatment of liquid fuel and the development therein ofsatisfactory anti-misting properties can usually be effected within atime interval of 15 minutes, which is compatible with most aircraftrefuelling schedules.

In cases, however, where it is desired to use amounts of amino compoundin the upper part of the range previously stated, say in the region of0.4-0.6 mole per 100 g of copolymer, or where complete freedom of choiceof the amounts of copolymer and amino compound respectively is required,and yet at the same time the speed of dissolution of the copolymer isimportant, it is desirable to operate steps (B) and (C) sequentially, sothat the copolymer is rapidly and fully dissolved before the aminocompound is introduced.

It is assumed, in the foregoing discussion, that the solubility of theamino compound in the liquid fuel is at least sufficient to enable thestated proportions to be attained of amino compound actually dissolvedtherein.

The invention is illustrated by the following Examples, in which parts,percentages and ratios are by weight:

EXAMPLE 1

An aqueous copolymer dispersion is prepared by polymerising a mixture oftert-butylstyrene, methyl methacrylate and methacrylic acid in theratios 83:10:7 in the manner described in Example 1 of BritishApplication No. 7,909,483, as follows.

To a polymerisation vessel fitted with nitrogen inlet extending belowthe liquid level there is charged:

    ______________________________________                                        Distilled water         1152   parts                                          Acetone                 288    parts                                          Sodium dioctylsulphosuccinate                                                                         9      parts                                          ______________________________________                                    

This charge is stirred until the surfactant has completely dissolved.There is then added 360 parts of a pre-mixed charge of monomer havingthe composition tertbutylstyrene 83%, methyl methacrylate 10% andmethacrylic acid 7%. The temperature of the reaction mixture is adjustedto 25° C. and a nitrogen sparge is started at the rate of 200 ml ofnitrogen per minute per Kg of total charge. After nitrogen has beenpassed for 5 minutes, there are added in the order stated the followinginitiator charges, prepared immediately prior to addition by dissolvingeach solid in the water:

    ______________________________________                                        Ammonium persulphate 0.18   part                                              Distilled water      9      parts                                             Sodium dithionite    0.3    part                                              Distilled water      9      parts                                             ______________________________________                                    

The nitrogen flow rate is then reduced to 50 ml per minute per Kg oftotal charge, and the temperature is maintained within the range 25°-30°C. for a total period of 6 hours counted from the addition of theinitiators, cooling as necessary in order to control the reactionexotherm. Finally there is added 18 parts of a 0.1% solution of n-octylmercaptan and stirring and nitrogen flow are then discontinued.

There is thus obtained an aqueous copolymer emulsion of solids contentapproximately 20% by weight and average particle diameter 0.05-0.1micron, having a relative viscosity of 1.70 and a differential orificeflow rate of 4.25 ccs per 30 seconds. This polymer emulsion is thenspray dried. 34 parts of the resulting powder are blended with a mixtureof 64.3 parts of 2-methyl pentane-2:4-diol and 1.7 parts of n-butylaminein a mixer suitable for handling viscous pastes. The resulting blend haspaste properties similar to those of toothpaste.

The following procedure illustrates the rapid dissolution of thepolymeric additive in aviation fuel.

1 part of the above blend is injected into 110 parts of AVTUR 50 whichis rapidly stirred during the addition. When the addition is complete,the stirring rate is reduced and the composition is gently agitated for15 minutes. The resulting solution has a relative viscosity of 1.66 andits differential orifice flow rate is 4.0. The concentration ofcopolymer in the solution is 0.3% and it contains 0.068 mole ofn-butylamine per 100 g of copolymer.

EXAMPLE 2

(A) The blending and dissolution procedure of Example 1 is repeated butwith the omission of the n-butylamine. The resulting solution has arelative viscosity of 2.0 and a differential orifice flow rate of 1.1.

(B) The procedure of Example 2(A) is repeated, with the addition to the110 parts of solution (after the copolymer-diol blend has completelydissolved) of 0.017 part of n-butylamine. The solution thus obtained hasa relative viscosity of 1.72 and a differential orifice flow rate of4.6.

EXAMPLE 3

The fuel solutions described in Example 1 and Example 2(B) are bothdiluted with further AVTUR 50 to a concentration of 0.1% of thecopolymer, and are then subjected to the test of resistance to mistingand ignition which is described in Example 1 of Specification No.1,384,536. No substantial ignition of the fuel is observed.

EXAMPLE 4

30 parts of spray-dried copolymer, prepared as described in Example 1,is hand-stirred into a blend of 63 parts of 2-methyl pentane-2:4-dioland 7 parts of morpholine to form a slurry.

1 part of the slurry is added to 99 parts of AVTUR 50, and the mixtureimmediately subjected to vigorous shaking for 30 seconds. On allowing tostand at rest for 20 minutes, the kerosene gradually loses turbidity andforms a substantially clear solution containing 0.3% of the copolymer.

The sample is further diluted with AVTUR 50 to a copolymer concentrationof 0.1% and subjected to the fire-test as described in Example 1 ofSpecification No. 1,384,536. There is no ignition of the ejected fuel.

EXAMPLE 5

The procedure of Example 4 is repeated, but replacing the morpholine byan equal amount of n-propylamine. A similar result is obtained to thatdescribed in Example 4.

EXAMPLE 6

A dispersion consisting of 34 parts of spray-dried copolymer obtained asdescribed in Example 1, 64.3 parts of 2-methyl pentane-2:4-diol and 1.7parts of n-butylamine is replaced by compounding in a twin Sigma-bladedmixer.

A sample of the dispersion is metered into a turbulent flow of Jet Afuel, in the proportion of 0.9 part dispersion:99.1 part fuel, andtransferred to a 10-gallon capacity tank, fitted to a rocket-propelledsled. Fifteen minutes after introducing the copolymer dispersion intothe fuel, the sled is fired along a track into arrester gear at 88meters per second, and the fuel is ejected through an array of ignitionsources. No ignition of the fuel occurs. A similar procedure, but usingunmodified Jet A fuel, results in a large fire-ball.

EXAMPLE 7

A dispersion consisting of 30 parts of spray-dried copolymer obtained asdescribed in Example 1, 67.44 parts of 2-methyl pentane-2:4-diol and2.56 parts of 2-ethyl-1-amino hexane is prepared as described in Example6.

A sample of the dispersion is metered into a turbulent flow of Jet A-1fuel in the ratio 1 part copolymer dispersion: 99 parts fuel andsubjected to the fire-test procedure described in Example 6. There is noignition of the ejected fuel.

We claim:
 1. A composition suitable for addition to a liquid aliphatichydrocarbon fuel in order to impart to the fuel a resistance towardsmist formation when the fuel is subject to conditions of shock, thecomposition comprising (A) a copolymer of a mixture of monomersconsisting of (i) at least 75% by weight of tert-butylstyrene as onemonomer, (ii) from 1% to 24% by weight of a second monomer selected fromthe acrylic and methacrylic esters of aliphatic monohydric alcoholscontaining from 1 to 4 carbon atoms, 2-ethoxyethyl methacrylate,acrylonitrile, vinyl acetate, styrene and vinyltoluene, and (iii) from1% to 10% by weight of methacrylic acid as a third monomer, theaggregate of monomers (i), (ii) and (iii) being 100% and the copolymerhaving the following characteristics:(a) it is soluble in AVTUR 50aviation kerosene; (b) a 0.3% by weight solution of the copolymer inAVTUR 50 aviation kerosene has a relative viscosity in the range 1.3 to2.6 and a differential orifice flow rate in the range 3 to 7 ccs per 30seconds,and (B) a hydroxylic liquid which is a non-solvent for thecopolymer or only a weak swellant therefor but which is miscible to theextent of at least 1% by weight with the fuel.
 2. A composition suitablefor addition to a liquid aliphatic hydrocarbon fuel in order to impartto the fuel a resistance towards mist formation when the fuel issubjected to conditions of shock, the composition comprising (A) acopolymer of a mixture of monomers consisting of (i) at least 75% byweight of tert-butylstyrene as one monomer, (ii) from 1% to 24% byweight of a second monomer selected from the acrylic and methacrylicesters of aliphatic monohydric alcohols containing from 1 to 4 carbonatoms, 2-ethoxyethyl methacrylate, acrylonitrile, vinyl acetate, styreneand vinyltoluene, and (iii) from 1% to 10% by weight of methacrylic acidas a third monomer, the aggregate of monomers (i), (ii) and (iii) being100% and the copolymer having the following characteristics:(a) it issoluble in AVTUR 50 aviation kerosene; (b) a 0.3% by weight solution ofthe copolymer in AVTUR 50 aviation kerosene has a relative viscosity inthe range 1.3 to 2.6 and a differential orifice flow rate in the range 3to 7 ccs per 30 seconds,(B) a hydroxylic liquid which is a non-solventfor the copolymer or only a weak swellant therefor but which is miscibleto the extent of at least 1% by weight with the fuel, and (C) from 0.01to 0.6 mole, based on each 100 g of copolymer, of an amino compoundselected from the group consisting of alkyl monoamines containing from 1to 12 carbon atoms, alkanolamines containing from 4 to 10 carbon atoms,aromatic amines and heterocyclic amines.
 3. A composition as claimed inclaim 1 or claim 2, wherein the hydroxylic liquid is2-methyl-2:4-pentanediol.
 4. A composition as claimed in claim 1 orclaim 2, wherein the copolymer constitutes from 30% to 40% by weight ofthe total composition.
 5. A composition as claimed in claim 2, whereinthe amount of the amino compound is from 0.02 to 0.2 mole per 100 g ofcopolymer.
 6. A composition as claimed in claim 2, wherein the aminocompound is a primary aliphatic amine containing from 3 to 10 carbonatoms.
 7. A composition as claimed in claim 6, wherein the aminecompound is n-butylamine.
 8. A fuel composition of improved resistancetowards mist formation comprising (1) a liquid aliphatic hydrocarbonfuel which is normally subject to mist formation when the fuel issubjected to conditions of shock and (2) an effective amount of amodifier which reduces said tendency to mist formation, said modifierbeing a composition comprising (A) a copolymer of a mixture of monomersconsisting of (i) at least 75% by weight of tert-butylstyrene as onemonomer, (ii) from 1% to 24% by weight of a second monomer selected fromthe acrylic and methacrylic esters of aliphatic monohydric alcoholscontaining from 1 to 4 carbon atoms, 2-ethoxyethyl methacrylate,acrylonitrile, vinyl acetate, styrene and vinyltoluene, and (iii) from1% to 10% by weight of methacrylic acid as a third monomer, theaggregate of monomers (i), (ii) and (iii) being 100% and the copolymerhaving the following characteristics:(a) it is soluble in AVTUR 50aviation kerosene; (b) a 0.3% by weight solution of the copolymer inAVTUR 50 aviation kerosene has a relative viscosity in the range 1.3 to2.6 and a differential orifice flow rate in the range 3 to 7 ccs per 30seconds,(B) a hydroxylic liquid which is a non-solvent for the copolymeror only a weak swellant therefor but which is miscible to the extent ofat least 1% by weight with the fuel, and (C) from 0.01 to 0.6 mole,based on each 100 g of copolymer, of an amino compound selected from thegroup consisting of alkyl monoamines containing from 1 to 12 carbonatoms, alkanolamines containing from 4 to 10 carbon atoms, aromaticamines and heterocyclic amines.
 9. A fuel composition as claimed inclaim 8, wherein the hydroxylic liquid is 2-methyl-2:4-pentanediol andthe amino compound is n-butylamine.